CN1050639C - Process for manufacturing shadow mask made of iron/nickel alloy - Google Patents

Process for manufacturing shadow mask made of iron/nickel alloy Download PDF

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Publication number
CN1050639C
CN1050639C CN95120173A CN95120173A CN1050639C CN 1050639 C CN1050639 C CN 1050639C CN 95120173 A CN95120173 A CN 95120173A CN 95120173 A CN95120173 A CN 95120173A CN 1050639 C CN1050639 C CN 1050639C
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CN
China
Prior art keywords
shadow mask
iron
nickel alloy
mask board
max
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Expired - Fee Related
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CN95120173A
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Chinese (zh)
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CN1133896A (en
Inventor
J·勃德里
M·法拉尔
J·F·逖尔斯
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Aperam Stainless Precision SAS
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Imphy SA
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Publication of CN1050639C publication Critical patent/CN1050639C/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J29/00—Details of cathode-ray tubes or of electron-beam tubes of the types covered by group H01J31/00
    • H01J29/02—Electrodes; Screens; Mounting, supporting, spacing or insulating thereof
    • H01J29/10—Screens on or from which an image or pattern is formed, picked up, converted or stored
    • H01J29/18—Luminescent screens
    • H01J29/20—Luminescent screens characterised by the luminescent material
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/02—Local etching
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
    • H01J9/02—Manufacture of electrodes or electrode systems
    • H01J9/14—Manufacture of electrodes or electrode systems of non-emitting electrodes
    • H01J9/142—Manufacture of electrodes or electrode systems of non-emitting electrodes of shadow-masks for colour television tubes
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/001—Heat treatment of ferrous alloys containing Ni

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrodes For Cathode-Ray Tubes (AREA)
  • Heat Treatment Of Sheet Steel (AREA)
  • Heat Treatment Of Articles (AREA)

Abstract

Process for the mfr. of an iron-nickel alloy shadow mask, comprising an alloy comprising (in wt.%): 35.5-37 Ni; max. 0.5 Co; max. 0.1 Cr; max. 0.1 Cu; max. 0.1 Mo; max. 0.1 V; max. 0.1 Nb; max. 0.1 Mn; 0.03-0.15 Si; max. 0.001 S; 0.0001-0.002 Ca; 0.0001-0.002 Mg; max. 0.005 Al; max. 0.01 O; max. 0.002 C; max. 0.005 N; max. 0.003 P; 0.001 H; max. 0.001 B.

Description

Shadow mask made of iron/nickel alloy
The present invention relates to be used for the shadow mask made of iron/nickel alloy of chromoscope.
Chromoscope generally includes shell with glass display window and the display screen that red, green and blue-light emitting body are set thereon.The shadow mask board that is drilled with a large amount of apertures is installed in the pipe, and faces display screen in short range.When teletron is worked, in pipe, produce the three beams electron rays by three electron beam gun, electron beam passes through the interior hole of shadow mask board along bombardment phosphorescence district.
The relative position of hole and twinkler is such, each beam bombardment corresponding to the phosphorescence district of rainbow so that imaging.
Yet quite a few of electronics interdicted by shadow mask board, and the kinetic energy of these electronics is converted into the heat energy that the shadow mask board temperature is risen.The shadow mask board thermal expansion meeting that produces owing to the temperature rising causes shadow mask board local deformaton, and this can destroy the relative position between hole and the corresponding twinkler.
This can cause the image color distortion.This distortion meeting flattens shadow mask board with showing more, thereby housing is in the electric current of teletron generation, and the display window of pipe is just more and more flat.
As everyone knows, can avoid this because the problem that heat effect produces by making shadow mask board with the material of utmost point low thermal coefficient of expansion.For example, this material is the iron/nickel alloy that contains 36% nickel of having an appointment.Yet the difficulty of senior mechanical property and rolling this material has limited their uses in this purposes.
From U.S. Pat 4,685,321 (EP-A 179,506) know, for the first time provide the thin slice of this material to be used to make shadow mask board, heat-treat and make its reduce at room temperature 0.2% yielding stress, reduce by 0.2% yielding stress in the above moulding of room temperature further to make its then.Iron/nickel alloy used in this technology has 1 * 10 -6K -1～1.5 * 10 -6K -1Between coefficient of linear expansion.The nickel of replacing part with the cobalt of 2%～12% (by weight) quantity can obtain the lower coefficient of expansion.
Yet, replace nickel to have many shortcomings with boring.On the one hand, cobalt is a kind of very expensive element, and on the other hand, cobalt can pollute in shadow mask board by the used chemical milling reagent in chemical corrosion agent cobalt hole.
The purpose of this invention is to provide a kind of method of making shadow mask made of iron/nickel alloy, this iron/nickel alloy does not contain or contains few cobalt, and it has and is lower than 0.9 * 10 -6K -1Coefficient of linear expansion and be easy to be rolled.
For this reason, problem of the present invention is to make the method for shadow mask board according to following content:
-the thin slice that provides cobalt that many uniform distribution holes are arranged, the chemical constitution that constitutes the iron/nickel alloy of this thin slice comprises (by weight):
35.5％≤Ni≤37％
Co≤0.50％
Cr≤0.1％
Cu≤0.1
Mo≤0.1％
V≤0.1％
Nb≤0.1％
Mn≤0.1％
0.03％≤Si≤0.15％
S≤0.001％
0.0001％≤Ca≤0.002％
0.0001％≤Mg≤0.002％
Al≤0.005％
O≤0.01％
C≤0.02％
N≤0.005％
P≤0.003％
H≤0.001％
B≤0.001% all the other be iron and owing to smelt unavoidable impurities; This chemical constitution satisfies following relational expression:
S≤0.02 * Mn+0.8 * Ca+0.6 * Mg and
Cr+Cu+Mo+V+Nb+Si≤0.15%-this thin slice is heat-treated to obtain the 112-88 by ASTMME, the granularity of 12.4 standard codes is more than or equal to the crystal grain of ASTM7;
-this thin slice is formed so that it has mask shape.
Preferable is to select chemical constitution in following ratio:
Si≤0.08％
Cr≤0.07％
Cu≤0.05％
Mo≤0.05％
Mn≤0.05％
O≤0.005％
N≤0.003％
S≤0.0005％
C≤0.005％
B≤0.0004％
In order to make the coefficient of expansion low as far as possible, nickel content must be between 35.9%～36.2%.
Temperature is remained between 750 ℃～850 ℃ heat-treats in nonoxidizing atmosphere.
The invention still further relates to by coefficient of linear expansion between 20 ℃～100 ℃ and be lower than 0.9 * 10 -6K -1The shadow mask board that constitutes of iron/nickel alloy, wherein the chemical constitution of iron/nickel alloy comprises (by weight):
35.5％≤Ni≤37％
Co≤0.5％
Cr≤0.1％
Cu≤0.1％
Mo≤0.1％
V≤0.1％
Nb≤0.1％
Mn≤0.1％
0.03％≤Si≤0.15％
S≤0.001％
0.0001％≤Ca≤0.002％
0.0001％≤Mg≤0.002％
Al≤0.005％
O≤0.01％
C≤0.02％
N≤0.005％
P≤0.003％
H≤0.001％
All the other are iron and the impurity that can not keep away owing to smelt for B≤0.001%, and this chemical constitution satisfies following relational expression:
S≤0.02 * Mn+0.8 * Ca+0.6 * Mg and Cr+Cu+Mo+V+Nb+Si≤0.15%
Preferable is that the iron/nickel alloy chemical constitution that constitutes shadow mask board is:
Si≤0.08％
Cr≤0.07％
Cu≤0.05％
Mo≤0.05％
Mn≤0.05％
O≤0.005％
N≤0.003％
S≤0.0005％
C≤0.005％
B≤0.0004％
Also preferred nickel content is between 35.9%～36.2%.
Finally, wish that iron/nickel alloy has the crystal grain of granularity (according to ASTM E112-88,12.4 measure) greater than the ASTM7 index.
To at length narrate the present invention now, but be not limited to this.
Obtain the light sheet that thickness is about 150 μ m by cold rolling then (by weight) following iron/nickel alloy ingot casting or the slab formed that contain of hot rolling:
35.5％≤Ni≤37％
Co≤0.5％
Cr≤0.1％
Cu≤0.1％
Mo≤0.1％
V≤0.1％
Nb≤0.1％
Mn≤0.1％
0.03％≤Si≤0.15％
S≤0.001％
0.0001％≤Ca≤0.002％
0.0001％≤Mg≤0.002％
Al≤0.005％
O≤0.01％
C≤0.02％
N≤0.005％
P≤0.003％
H≤0.001％
B≤0.001% all the other be iron and owing to smelt unavoidable impurities; This chemical constitution satisfies following relational expression:
S≤0.02 * Mn+0.8 * Ca+0.6 * Mg and Cr+Cu+Mo+V+Nb+Si≤0.15%
Select the composition of this alloy so that its coefficient of linear expansion is lower than 0.9 * 10 -6K -1, preferably be lower than 0.8 * 10 -6K -1, have hot rolling and cold rolling suitability, obtain to have very meticulous and minimum spacing and be distributed in the suitability of the hole on the monoblock thin plate by chemical milling, and the suitability of drawing cold shaping.
Make the content of nickel, chromium, copper, molybdenum, vanadium, niobium, silicon and manganese meet following relational expression:
Cr+Cu+Mo+V+Nb+Si≤0.15% is lower than 0.9 * 10 to reach coefficient of linear expansion -6K -1Preferred nickel content is between 35.9%～36.2% (by weight); Chromium content (by weight) is lower than 0.07%; Copper, molybdenum, manganese content be lower than 0.05% and silicone content be lower than 0.08%; Thereby obtain being lower than 0.8 * 10 -6K -1Coefficient of linear expansion.
Cobalt contents must keep below 0.5% so that prevent to pollute the etching reagent of chemical milling operation usefulness.
Make the limit of sulphur, silicon, calcium, magnesium, aluminium, oxygen and phosphorus content meet following relational expression:
S≤0.02 * Mn+0.8 * Ca 10 * Mg ignores extremely low manganese content to obtain good rollability.Preferablely be, oxygen level must be lower than 0.005%, and sulphur content is lower than 0.0005%.
Aluminium content must be lower than 0.005%, nitrogen content is lower than 0.005%, is preferably lower than 0.003%, so that prevent to generate aluminium nitride, because this is disadvantageous to hot workability.
Carbon content must keep below 0.02%, is preferably lower than 0.005%, so that reduce yielding stress.This is favourable to malleability.
Oxygen level is limited in 0.001% to prevent bubble.
Boron content must keep below 0.001%, preferably be lower than 0.0004%, generates easily crisp nitride so that during heating treatment prevent thin sheet surface.
In band, form the hole of very fine by the chemical light engraving method.These holes may have any desirable shape, for example circle or elongated shape.
After etching hole, the also etched thereon sheet material that goes out defiber is divided into thin slice, and the above-mentioned thin slice that constitutes the shadow mask thin slice comprises several rows of hole.
The material of gained formation shadow mask thin slice at room temperature has 0.2% yielding stress (between 580MPa～640MPa) thus, and this is too high concerning the shadow mask thin slice that obtains required curvature.In order to reduce this yielding stress, this shadow mask thin slice under temperature between 750 ℃～850 ℃ in hydrogeneous atmosphere (about 10% H 2, all the other are N 2) in annealing about 15 minutes, the material that obtains thus, it have granularity be about 15 μ m crystal grain, be about the coercive force of 40A/m and between 20 ℃～100 ℃ coefficient of linear expansion be less than or equal to 0.9 * 10 -6K -1
Although reduced yielding stress, yet for making shadow mask board become repeatably method, it is too high that the yielding stress of 280MPa is still disliked.The result must further reduce yielding stress.In order to accomplish this point, the shadow mask thin slice is shaped.Under 200 ℃, yielding stress is about 130MPa.
As an example, the material with following chemical constitution used according to the invention is made shadow mask board:
Ni＝36.13％
Co＝0.015％
Cr＝0.02％
Cu＜0.01％
Mo＝0.0055％
V＜0.005％
Nb＜0.005％
Si＝0.078％
Mn＝0.024％
S＜0.0005％
Ca＝0.0003％
Mg＝0.0004％
Al＜0.005％
O＝0.0042％
C＝0.003％
N＝0.0033％
P＜0.003％
H＜0.001％
B＜0.0004％
By each represented content of " being lower than " is content below used analytical technology sensitivity threshold.
The local convex defective of gained shadow mask board lacks at least 15% than observed similar defective on the shadow mask made of iron/nickel alloy of making according to prior art as a comparison thus.
Because cobalt contents is low, this element does not influence chemically etching process.In case pipe is energized, the coercive field that is lower than 55A/m is for the process particularly advantageous that makes used shadow mask board demagnetization.
One of advantage of the present invention is, need not in order to place restrictions on the heating that electron-bombardment causes and uses Bi 2O 3, Al 2O 3One type coating or lead borate glass apply shadow mask board.
The present invention relates to have the shadow mask board of circle or elongated shape hole, these holes are as expanding equably in the focal length at shadow mask board well on the total length of shadow mask board.This shadow mask board is suitable for making chromoscope especially, and this shadow mask board has the minimum hole of a large amount of spacings.
Should be noted that according to the present invention the shadow mask thin plate that particularly contains minute quantity Si, Mn and Cr has more uniform crystal structure, this can improve chemical milling.This is concerning very important as the shadow mask board of chromoscope, because this shadow mask board must have the minimum a large amount of holes of spacing.

Claims (4)

1. one kind is lower than 0.9 * 10 by coefficient of linear expansion between 20 ℃～100 ℃ -6K -1The shadow mask board that constitutes of iron/nickel alloy, it is characterized in that iron/nickel alloy has following composition (by weight):
35.5％≤Ni≤37％
Co≤0.5％
Cr≤0.1％
Cu≤0.1％
Mo≤0.1％
V≤0.1％
Nb≤0.1％
Mn≤0.1％
0.03％≤Si≤0.15％
S≤0.001％
0.0001％≤Ca≤0.002％
0.0001％≤Mg≤0.002％
Al≤0.005％
O≤0.01％
C≤0.02％
N≤0.005％
P≤0.003％
H≤0.001％
B≤0.001％
All the other be iron and owing to smelt unavoidable impurities; This chemical constitution satisfies following relational expression:
S≤0.02×Mn+0.8×Ca+0.6×Mg
With
Cr+Cu+Mo+V+Nb+Si≤0.15％，
And the crystal grain of described iron/nickel alloy has the granularity greater than ASTM 7 indexs.
2. according to the shadow mask board of claim 1, it is characterized in that this shadow mask board is lower than 0.8 * 10 by coefficient of linear expansion between 20 ℃-100 ℃ -6K -1Iron/nickel alloy constitute.
3. according to the shadow mask board of claim 1 or 2, it is characterized in that in the chemical constitution of described iron/nickel alloy (by weight):
Si≤0.08％
Cr≤0.07％
Cu≤0.05％
Mo≤0.05％
Mn≤0.05％
O≤0.005％
N≤0.003％
S≤0.0005％
C≤0.005％
B≤0.0004％。
4. according to the shadow mask board of claim 1 or 2, it is characterized in that, in the chemical constitution of iron/nickel alloy (by weight):
35.9％≤Ni≤36.2％。
CN95120173A 1994-12-27 1995-12-26 Process for manufacturing shadow mask made of iron/nickel alloy Expired - Fee Related CN1050639C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9415663 1994-12-27
FR9415663A FR2728724B1 (en) 1994-12-27 1994-12-27 METHOD FOR MANUFACTURING AN IRON-NICKEL ALLOY SHADOW MASK

Publications (2)

Publication Number Publication Date
CN1133896A CN1133896A (en) 1996-10-23
CN1050639C true CN1050639C (en) 2000-03-22

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CN95120173A Expired - Fee Related CN1050639C (en) 1994-12-27 1995-12-26 Process for manufacturing shadow mask made of iron/nickel alloy

Country Status (9)

Country Link
US (1) US5643697A (en)
EP (1) EP0719873B1 (en)
JP (2) JPH08333638A (en)
KR (1) KR100379871B1 (en)
CN (1) CN1050639C (en)
DE (1) DE69517577T2 (en)
DK (1) DK0719873T3 (en)
FR (1) FR2728724B1 (en)
PL (1) PL186742B1 (en)

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JP3360033B2 (en) * 1998-10-22 2002-12-24 日新製鋼株式会社 Fe-Ni alloy for shadow mask and method for producing the same
TWI225101B (en) * 1999-03-12 2004-12-11 Toyo Kohan Co Ltd Material for shadow mask, method for production thereof, shadow mask and image receiving tube
JP2001131709A (en) * 1999-11-09 2001-05-15 Nippon Mining & Metals Co Ltd LOW THERMAL EXPANSION Fe-Ni SERIES ALLOY FOR SEMITENSION MASK, SEMITENSION MASK USING THE SAME AND COLOR CATHODE- RAY TUBE
JP2001131715A (en) * 1999-11-09 2001-05-15 Nippon Mining & Metals Co Ltd Fe-Ni SERIES ALLOY FOR SEMITENSION MASK, SEMITENSION MASK USING SAME AND COLOR CATHODE-RAY TUBE
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DE10146301C1 (en) * 2001-09-19 2002-07-18 Krupp Vdm Gmbh Production of a strip made from an iron-nickel alloy, used for shadow masks in flat monitors and TV screens, comprises continuous or batch-type annealing a strip made from an iron alloy containing nickel, molybdenum and chromium
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FR2849061B1 (en) * 2002-12-20 2005-06-03 Imphy Ugine Precision FER-NICKEL ALLOY WITH VERY LOW THERMAL EXPANSION COEFFICIENT FOR THE MANUFACTURE OF SHADOW MASKS
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EP0561120A1 (en) * 1992-01-24 1993-09-22 Nkk Corporation Thin Fe-Ni alloy sheet for shadow mask and method for manufacturing thereof
EP0567989A1 (en) * 1992-04-27 1993-11-03 Hitachi Metals, Ltd. Shadow mask sheet, method of producing the same and cathode ray tube provided therewith
EP0626462A1 (en) * 1993-05-27 1994-11-30 Krupp VDM GmbH Iron-nickel alloy with low thermal expansion coefficient
EP0627494A1 (en) * 1993-05-31 1994-12-07 Nkk Corporation Alloy sheet for shadow mask and method for manufacturing thereof

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CN1133896A (en) 1996-10-23
FR2728724A1 (en) 1996-06-28
EP0719873B1 (en) 2000-06-21
JP2007231423A (en) 2007-09-13
EP0719873A1 (en) 1996-07-03
PL186742B1 (en) 2004-02-27
KR100379871B1 (en) 2003-06-19
FR2728724B1 (en) 1997-01-24
DK0719873T3 (en) 2000-10-23
DE69517577D1 (en) 2000-07-27
JPH08333638A (en) 1996-12-17
KR960026015A (en) 1996-07-20
DE69517577T2 (en) 2001-03-08
PL312029A1 (en) 1996-07-08
US5643697A (en) 1997-07-01

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